N 1-substituted-3-haloindazoles and their use as pesticides

ABSTRACT

Compounds that have the structural formula   WHEREIN X represents   -SCY3, or -CH2-Z; Y represents halogen; Y&#39;&#39; represents halo-lower alkyl or halophenyl; Z represents halogen, -SCN, -CH2OH, -CH2Y,   -NR-N(R)2, or -N (CH2)m; R represents hydrogen or lower alkyl; m represents an integer in the range of 4 to 8; and n represents an integer in the range of 0 to 1 are used to control the growth of various plant and animal pests.

United States Patent 1 Minieri [451 June 26, 1973 N 1-SUBSTITUTED-S-HALOINDAZOLES AND THEIR USE AS PESTICIDES [75] Inventor: Pasquale P. Minieri, Woodside, N.Y.

[73] Assignee: Tenneco Chemicals, Inc., Saddle Brook, N, J.

52 US. Cl 260/310 C, 7 1/92, 424/273 51 Int. cl C07d 49/18' [58] Field of Search 260/310 C [56] References Cited FOREIGN PATENTS OR APPLICATIONS 4/1969 France 260/310 C OTHER PUBLICATIONS Pozharskii et al. J. Gen. Chem. (USSR) Vol. 34, page 3409-11 (1964). QD1.Z6a

Auwers Liebigs Ann. Chem. Vol. 527, pages 291-8 (1937). QDl.L7

Auwers et al. Liebigs Ann. Chem. Vol. 438, pages 14-23 relied on (1924). QDI.L7

wherein X represents Erik/dr ErdminerNatalie 1301153?" m Attorney-Daniel J. Reardon, Barry G. MagidofflEvelyn Berlow and James P. Scullin ABSTRACT Compounds that have the structural formula sents halo-lower alkyl or halophenyl; Z represents haloor lower alkyl; m represents an integer in the range of 4 to 8; and n represents an integer in the range of 0 to 1 are used to control the growth of various plant and animal pests.

3 Claims, No Drawings N l-SUBS'IITUTED-3-IIALOINDAZOLES AND THEIR USE AS PESTICIDES This is a continuation-in-part of my copending U.S. Pat. application Ser. No. 87,615, which was filed on Nov. 6, I970.

This invention relates to certain N-substituted-3 halo-indazoles and to the use of these compounds in the control of various plant and animal pests.

in accordance with this invention, it has been found that certain N -substituted-B-haloindazoles have unusual and valuable activity as fungicides, as herbicides, and as bactericides. These compounds may be represented by the structural formula SCY or -CH Z; Y represents chlorine, bromine, fluorine, or iodine; Y represents a chloro-, brom'o-, fluoro-, or iodolower alkyl or phenyl group; Z represents chlorine, bromine, fluorine, iodine, -SCN, -CH OH, -CH Y',

-NRNR or 'N=(CH R represents hydrogen or a lower alkyl group;-m represents an integer in the range of 4 to 8; and n represents an integer in the range of zero to 2.

Particularly effective as pesticides are the compounds having the aforementioned structure in which Y represents chlorine. Illustrative of these preferred compounds are the following: N- trichloromethylmercaptomethyl-3-chloroindazole, N- (p-chlorobenzoyl)-3-chloroindazole, N-(2,6- dichlorobenzoyl)-3-chloroindazole, N-('2,3,6- trichlorobenzoyl)-3-chloroindazole, N -(2-hydroxyethyl)-3-chloroindazole, N -chloromethyl-3- chloroindazole, N -thiocyanatomethyl-3- chloroindazole, N -chloroacetyl-3-chloroindazole, N- chloroacetoxymethyl-3-chloroindazole, l-(3- chloroindazolyl-N'-methyl)-2,2,-dimethylhydrazine, N-(3-chloroindazolyl-N -methyl)- hexamethyleneimine, (3-chloroindazolyl-N -methyl)- N-methylcarbamate, and the like;

The N-substituted-3-haloindazoles of this invention may be prepared by any suitable and convenient procedure. For example, they may be prepared by heating the appropriate substituted indazole with a compound that will react with it to form the desired N -substituted-3-haloindazole; Thus 3-chloroindazole may be heated with trichloromethylsulfenyl chloride to form N -trichloromethylmercapto-3-chloroindazole, and N- hydroxymethyl-3-chloroindazole may be heated with l,l-dimethylhydrazine to form l-(3-chloroindazolyl- N'-methyl)-2,2-dimethylhydrazine. The reactions are generally carried out in a solvent, such as benzene, toluene, acetone, pyridine, chloroform, ethanol, or ethylene dichloride, at the reflux temperature of the reaction mixture.

' cent to 60 percent by weight of a water-insoluble resin- The N-substituted-3-haloindazoles may be applied to a wide variety of fungi. bacteria, and plants to control or inhibit their growth.

In a preferred embodiment of the invention, the N- substituted-3-haloindazoles are used to impart fungal and bacterial resistance to surface-coating compositions including both organic solvent-based and waterbased coating systems. They are particularly valuable as biocides in coatings that contain as their resinous binder either an oleoresinous material or a waterinsoluble synthetic linear addition polymer.

Among the surface coating compositions in which the compounds of this invention can be used as the biocide are organic solvent-based systems that contain such oleoresinous binders as drying oils, for example, linseed oil,-tung oil, soybean oil, dehydrated castor oil, safflower oil, or fish oil; bodied drying oils; blends of drying oils or bodied drying oils with a resin component, such as limed rosin, ester gum, phenolic resins; oleoresinous varnishes formed by heating the aforementioned resins with drying oils or bodied drying oils; and alkyd resins.

The novel compounds may also be used as the biocide in aqueous dispersions that contain about 10 perous binder that is'an oleoresinous' binder as hereinbefore defined and/or a synthetic linear addition binder. The aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerizationv of ethylenically unsaturated compounds, especially those of monoethylenically unsaturated character, although butadiene, .chlorobutadiene, and isoprene maybe used to some extent. Illustrative of the synthetic linear addition'polymers that can be used as the resinous binder in the aqueous dispersions are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl chloride with vinyl acetate, vinylidene chloride, acrylonitrile, methacrylic acid and methacrylic acid esters, acrylic acid'and acrylic acid esters; polyethylene; polyisobutylene; polystyrene; copolymers of styrene with butadiene, acrylicacid esters, methacrylic acid esters, or maleic anhydride; and the like.

Only a small 5 amount of the N '-substituted-3- haloindazole need be present in the surface-coating compositions. As little as 0.10 percent'of one or more of these compounds, based on the weight of the composition, willbring about an appreciable improvement in the resistance of the composition to attack by microorganisms. Three percent or morecan be used, but these larger amounts generally do' not provide furtherimprovement' in the properties of the surface-coating compositions and for this reason are not ordinarily used. In most cases about 1 percent to 2 percent of the biocidal compound, based on the weight of the surfacecoating composition, is used. g

In another preferred embodiment of the invention, the N -substituted-3-haloindazoles are used as agricultural fungicides. Theycan be applied to plants or to the soil in'which plants are growingto control the growth of a number of plant pathogens without causing visible injury to the plants. In addition they may be usedas post emergence selective-herbicides.

The inventionis further illustrated by the examples that follow. I l

EXAMPLE 1 A. A mixture of 45 grams (0.296 mole) of 3- chloroindazole, l 1.1 grams (0.369 mole) of paraformaldehyde, 200 ml. of ethanol, and 2.3 ml. of 5 percent aqueous sodium hydroxide solution was heated at its reflux temperature for about 3 hours, cooled, and filtered. The solid product, which was N-hydroxymethyl- 3-chloroindazole, was washed with water and dried.

B. A mixture of 36 grams (0.2 mole) of N- hydroxymethy1-3chloroindazole, 19 ml. (0.25 mole) of thionyl chloride, and 250 m1. of ethylene dichloride was heated at its reflux temperature for 3 hours and then cooled to room temperature. The reaction mixture was heated under reduced pressure on a water bath to remove ethylene dichloride. Benzene (250 ml.) was added to the residue, and the resulting solution was heated under reduced pressure on a water bath to remove the solvent. The addition of benzene and its removal by heating under vacuum were repeated until a constant weight of product was obtained. There was obtained 39.5 grams of N -chloromethyl-3- chloroindazole, which melted at 7482 C. and which contained 49.76 percent C, 3.22 percent H, and 14.52 percent N (calculated, 47.8 percent C, 2.98 percent H, and 13.92 percent N).

EXAMPLE 2 A mixture of 20.1 grams (0.1 mole) of N- ch1oromethyl-3-chloroindazole, 9.7 grams (0.1 mole) of potassium thiocyanate, and 200 ml. of acetone was heated at its reflux temperature for 3 hours, cooled to room temperature, and allowed to stand overnight. After filtration, the filtrate was heated toremove the acetone. The residue, which crystallized on standing, was dissolved in 100 ml. of ethyl acetate. The solution was washed with 25 ml. of water and then heated to remove the solvent. There was obtained 20.3 grams of N- -thiocyanatomethyl-3-chloroindazole, which melted at 40-5 3 C. and contained 48.9 percent C, 2.97 percent H, and 18.38 percent N (calculated, 48.3 percent C, 2.02 percent H, and 18.78 percent N).

EXAMPLE 3 To a mixture 'of 18.1 grams (0.1 mole) of N- hydroxymethyl-3-chloroindazole, 1 ml. of triethylamine, and 150 m1. of tetrahydrofuran was added 6.4 grams (0.133 mole) of methyl isocyanate over a period of about minutes during which time its temperature rose from 22 C. to 26 C. The reaction mixture was heated to its reflux temperature in minutes and held at this temperature for 75 minutes. 1t was cooled and allowed to stand overnight at room temperature. It was then cooled in an ice bath and filtered. The product was dried at 60 C. under reduced pressure. There was obtained 15.6 grams of (3-chloroindazolyl-N -methyl) N-methyl-carbamate, which melted at 16ll67 C.

EXAMPLE 4 cooled in-a'n ice bath and filtered. The product was dried at 50 C. under vacuum. There was obtained 9.9 grams of l-(3-chloroindazolyl-N -methyl)-2,2-dimethylhydrazine, which melted at l45-150 C.

The filtrate was evaporated to dryness under reduced pressure on a water bath. The residue was crystallized from 35 ml. of toluene and dried at 50 C'. under reduced pressure to yield an additional 4.0 grams of the product, which melted at l45-l50 C.

The two crops of the product were combined and analyzed. The 1-(3-chloroindazolyl-N-methyl)-2,2-dimethylhydrazine contained 54.25 percent C, 2.98 percent H, and 18.23 percent N (calculated, 56.8 percent C, 6.2 percent H, and 19.9 percent N).

EXAMPLE 5 Using the procedure described in Example 4, 18.3 grams (0.1 mole) of N -hydroxymethyl-3- chloroindazole was reacted with 10 grams (0.1 mole) of hexamethyleneimine. The reaction mixture was heated on a water bath under reduced pressure until it reached constant weight. There was obtained 27.7 grams of N-(3-chloroindazolyl-N-methyl)hexamethyleneimine, which contained 63.35 percent C, 6.51 percent H, and 15.62 percent N (calculated, 65.2 percent C, 6.52 percent H, and 15.23 percent N).

EXAMPLE 6 To a mixture of 18.2 grams (0.1 mole) of N hydroxymethyl-3-chloroindazole, 1 1.1 grams (0.1 1 mole) of triethylamine, and 200 ml. of benzene was added dropwise a solution of 12.4 grams (0.11 mole) of chloroacetyl chloride in 25 ml. of benzene. The reaction mixture was allowed to stand at room temperature for minutes and was then heated at its reflux temperature for 5 minutes. It was cooled to room temperature and then cooled in an icebath. 7

After filtration, the filtrate was washed with two ml. portions of water. Upon drying under reduced pressure on a water bath, there was obtained 23.2 grams of N -chloroacetoxymethyl-3-chloroindazole, which contained 45.41 percent C, 3.10 percent H, and 10.71 percent N (calculated, 46.2 percent C, 3.09 percent H, and 10.76 percent N).

EXAMPLE 7 A mixture of 18.1 grams (0.1 mole) of 3- chloroindazole, 7.9 grams (0.127 mole) of ethylene carbonate, and 0.1 1 gram of anhydrous potassium carbonate was heated at 150 C. for 5 hours and then allowed to stand overnight at room temperature. The solidified reaction mixture was heated in 40 ml. of benzene until it had dissolved. The solution was cooled and filtered. After washing and drying, there was obtained 7.0 grams of N-(2-hydroxyethyl)-3-chloroindazole, which melted at 113 C.-l26 C. which contained 53.69 percent C, 3.66 percent H, and 16.15 percent N (calculated, 55.0 percent C, 4.58 percent H, and 14.2 percent N).

EXAMPLE 8 To'a mixture of 28 grams of 3-chloroindazole, 17.7 grams of triethylamine, and 250 ml. of benzene which was beingheated at its reflux temperature was added over a period of 40 minutes 34.4 grams of trichloromethanesulfenyl chloride. The resulting mixture was heated at its reflux temperature for 2.5 hours,cooled to room temperature, and filtered. The filtrate was washed with two 100 ml. portions of water and then heated to remove the benzene. The N- trichloromethylmercapt-3-chloroindazole obtained was a liquid that contained 33.0 percent C, 1.48 percentl-l, and 9.56 percent N (calculated, 31.7 percent C, 1.32 percent H, and 9.22 percent N).

EXAMPLE 9 then cooled in an icebath. The precipitated solid material was separated by filtration and air-dried. There was obtained 18.5 grams of N-(3,4-dichlorobenzoyl)-3- chloro-indazole, which melted at l44l46 C.

The mother liquor was washed twice with water and then evaporated to dryness. The residue was crystallized from benzeneto yield an additional 6.8 grams of crude product. This product was stirred with 5 percent aqueous sodium carbonate solution. The product was separated by filtration, washed with water, and dried.

EXAMPLE To a mixture of' 8.53 grams (0.05 mole) of 3- chloroindazole, 8 ml. (0.05 mole) of triethylamine, and 100 ml. of benzene which had been heated to its reflux temperature was added over a period of ten minutes 4.5 ml. (0.058 mole) of chloroacetyl chloride. The reaction mixture was heated at its reflux temperature for 2 hours and then filtered while hot. The filtrate was heated under reduced pressure at 50C. to remove the benzene. The solid product obtained when the residue was cooled was dissolved in 200 ml. benzene; the resulting solution was washed with water and then with carbon tetrachloride. Upon removal of the benzene, there was obtained 12 grams 'of-N -chloroacetyl-3- chloroindazole'that melted at 74.0-84.5 C. and that contained 46.72 percent C, 2.87 percent H, 11.87 percent N, and 29.52 percent Cl (calculated, 47.2 percent C,- 2.62 percent H, 12.2 percent N, and 31.0 percent CI).

EXA PLE 11 A. A polyvinyl acetate emulsion paint was prepared by mixing together the following materials:

Parts by Weight 280 55% Aqueous dispersion of polyvinyl acetate There was obtained 5.8 grams of material that melted To samples of this paint was added either 2 percent by weight of one .of the compounds of this invention or 2 percent by weight of a comparative biocide.

B. An acrylic paint wasprepared by mixing together the following materials: 1

Parts by Weight Water 250 Acrylic acid resin solids)(Acryloid B-66) 385 Monoethyl ether of ethylene glycol 259 Titanium dioxide 143 Aluminum silicate 45 Magnesium silicate 98 To samples of this paint was added either 2 percent by weight of one of the compounds of this invention or 2 percent by weight of a comparative biocide.

C. An exterior house paint was prepared by mixing together the following materials:

Parts by Weight Antiskinning agent (Exkinv 2) 2 Manganese naphthenate (6%) 2.27 Lead naphthenate (24%) l 1.3

To samples of this paint was added 2 percent by weight of either one of the compounds of this invention or a comparative biocide.

EXAMPLE 12 Samples of the acrylic paint, the polyvinyl acetate paint, and the oil-based paint whose preparation was described in Example 1 l were evaluated by the following procedure: Pieces of drawdown paper were dipped into the paint, dried for 24 hours, and again'dipped into the paint. After a 24-hour drying perod, the coated paper samples were cut into 1% inch squares. Each of the coated paper squares was placed on a plate of malt and mycophil agar, which had been inoculated with 1 ml. of a suspension of the test organism. The plates, prepared in triplicate, were incubated at 28C. and observed weekly. The growth was estimated according to the following key, and the results of the triplicate plates were averaged. In the tables that follow ZO Zone of inhibition in mm.

O No zone of inhibition Tr Trace of zone of inhibition Not tested Bacteria A Bacillus subtilis B Aerobacter aerogenes C Pseudomonas aeruginosa Fungi D Pullularia pullulans I E Penicillium crusrosum F Aspergillus niger The biocidal compounds tested and the tained are set forth inTable l.

EXAMPLE l3 N -Trichloromethylmercapto-3-chloroindazole was evaluated as a post-emergence herbicide byspraying seedlings of various plant species'with an aqueous solu-, tion that contained 1000' ppm of the test compounds and observing the results after 43 days. A numerical results obscale is usedin Table ll to show the herbicidal activity TABLE Ill of this compound. On this scale 1 indicates that no in- Activity of jury was caused to the plants, 2 indicates slight injury, N -Trichloromethylmercapto-3-chloroindazole as a 3 indicates moderate injury, 4 indicates severe injury, Soil Fungicide and 5 indicates that all plants were killed. 5

EXAMPLE l4 Separate lots of sterilized soil were inoculated with plant pathogens. The inoculated soil was placed in 4- Rate of Rhizo- Application Sclemlium Pythium cmnia Fusannm ounce containers, and the soil in each container was (b/acre) mm v oxmwmm drenched with ml. of an aqueous solution of N 300 s 5 4 V 5 trichloromethylmercapto-3-chloroindazole. Afterincu 4 1 4 3 a 75 i 2 I i 1 bation for two days at 70 F., the amount ofmycelial growth on the surface of the soil was noted. The results of these tests are given in Table III. In this table a rating 15 of 1 indicates that the surface of the soil was completely covered with colonies of the organism, 2 indi- The terms and expressions which have been emcates that about 75 percent of the surface was covered ployed are used as terms of description and not of limiwith colonies of the organism, 3 indicates that about tation. There is no intention in the use of such terms half of the surface was covered with colonies of the or- 20 and expressions of excluding any equivalents of the feaganism, 4 indicates that a few scattered colonies were tures shown and described or portions thereof, but it is present, and 5 indicates that there was no mycelial recognized that various modifications are possible growth on the surface of the soil. within the scope of the invention claimed.

.&.a e A EASE ,f, WWW,

Biocidul activity Bacteria Fungi Effect on Biocidc Paint pH paint odor A B C D E F 7 Acrylic Product of Example 1 .{gjiA l Acrylic Product of Example2 Acidic .11: Product of Exampleii {PVA I Oil do 0 0 '0 Acryllc 9.1 Moderate. 0 (l 0 20-2 'll()7 Z0-1 lroductofExumplc4 (1 720-5 Tr 730-5 7.0-2 zo-a 20-1 Product of Example IL, Z045 20-2 20-5 20- 20-3 Product)!Exumplufin ,.{P A 7.0-6 Tr u 0 Product. of Example 7. (I 0 zo-n 7.0a J 7.0-2 zo-a Product of Exzilllplu it Z0 .2 7.0-3 7,01 x0e:

('I 2,3,5,6-tetrauliloroi-(nmthylsulionyl)-pyridiim (Dow 1013) ZO-IO 7.0-6 20*10 zo u TABLE ll What is claimed is: Activity of l. A compound having the structural formula N-Trichloromethylmercapto-3-chloroindazole as a Post-emergence Herbicide I CY Herbicidal Activity Rate of Application (lb/acre) 20 1O 5 \N/ Plant Species (I:

Clover 4 3 2 O: VY' Soybean 3 2 2 Sugar Beet 4 4 3 1 Cotton 2 2 2 wherein Y represents halogen and Y represents halo- 2 2 2 lower alkyl or halophenyl. Oats s 2 1 Mustard 5 3 1 2. The compound as set forth in claim 1 that isN Morning Glory 2 2 1 (3,4-dichlorobenzoyl)f3-chloroindazole. gzg ggz i g f 3. The compound as set forth in claim 1 that is N- crab Grass 5 2 l chloroacetyl-3-chloroindazole. Fox Tail 3 2 2 

2. The compound as set forth in claim 1 that is N1-(3,4-dichlorobenzoyl)-3-chloroindazole.
 3. The compound as set forth in claim 1 that is N1-chloroacetyl-3-chloroindazole. 